Vinyl resin-alkyd wrinkle composition



March 2, 1954 W. A. WALDIE VINYL RESIN-ALKYD WRINKLE COMPOSITION FiledDec. 8, 1950 FINELY GROUND ALKYD TYPE VINYL RESIN RESIN DISPERSION MIXAND GRIND FINELY cnouuo PLASTIOIZER ,AND TO VINYL PASTE VINYL RESINDISPERSING AGENT ALKYD TYPE VINYL RESIN RESIN DISPERSION DISPERSION MIXAND GRIND I E T0 VINYL PASTE I PIGMENT FILLER ALKYD RESIN DISPERSIONVINYL PASTE MIX AND GRIND T0 WRINKLING COMPOSITION SPRAY BAKE AT sodF.

INVENTOR WILLIAM .A. WALDIE ATTORNEYS Patented Mar. 2, 1954 UNITEDSTATES amines QQMROSITI i i. WiiliamA. Waldie; Day-ton, Qhig a i NewWrinkle rmione acpmnaiise; ,1:- Delaiware v v A i icaiiptllne tmhcr s,19 seriahNo? 199,788? 1&Glaims; (CL gg 1 2. This invention relates towrinkle coating-cormprovide a. wrinkle coating composition hazingpositions and more partinul'arrltoto a Wrinke coatvinyl: resin.containeitherein; and wh chhas sub ing; composition; containing-vinylstantially noglosswhem baked; v

Vinyl resins are of seyeral (151 known a the acetates, butyraiiesi r-1neach thes s hfii 'l Q fls mli s ifil comppnentsrsunh m anhydride. Theproperties of each of these resins vary a to solubility, viscosity in,spin t e m sc bi ity w th.oi1s,,va ishes, oth

Itis: ano h r. important: objector: this invenw tion; to providealwninkle coating composition having a vinyl resin contained therein maybe baked to a hard film in a short period Of time.

a. futile; abjec Q his ipsv t 2 39 e lov-vide a Wrinkle coat on corn andalkyd's, this latter factor being particularly vinyli esincontainedpertinent in the formation otwrinkle coatings. Senate-hp oj filrn Asagenerar rule even a Tow concentration of; It is also an object of thisinvention pro; a vinyl" resin in a. solvent produces a viscous solu videa wrinkle coating composition having a vinyl tion which oanonly beappliedito surfaces totbe 151.19 contained therein which forms a non-COEITQdLWithLEnd-DCtOI' blade or a liOllflGfiiIfiIk tie rjinopl-asticwrinkle upon baking;

While the, solvent utilized in. the solution has These-and otherobjectsare accomplished by a definite bearing on the viscosity of such avinylrinding a finely divided-- vinyl resin withan resin. solution even lowviscosity solutions t nd all type resin solution, having the property tofeather when applied spraying Accord- 201 of-w J k-linewi-th-drier-,-tofo1=rnavinyipastefand ingly such vinyl resins have notbe considered m'HLng-thispaste with color-ingmaterial drier, generallysatisfactory for the iorn' a on; qr; wrinsolvent and further alkyd resinas required The kle coatings and have beenconsidered'particwcompositionresul inefrom-su h-a mi e may larly unsatisfactory where itis desired to spray be ehd l sprayed ar dfiatlitfq the wrinkle coating.

n m ie-n edin se ieetiqa, ti i meant. the Qet bei' wr ewtl a. method, ofsolving, th

using solutions of vinyl re t referred t at t e of th est t p ly nyl hlrid resin when added, as a powder ha m the range of about 1 to 30microns in diameter with a mean diameter; of:

t W-LI m T composition having a Vinyl re n o 0=micr0n-si Insome.nstances 1t mast be de- Out the necessity of using a vinyl resin smutenable. to. firstdmperse. the, polyvinyl chloride is a fu the OM66; ofthis inven '1 resin in. asuitablehydrocarbonand add aplasprovidewrmkiecoatmg -dhfi' m a tiei zer thereto to facilitate the mixing of thevinyl resin therein and whi h @5 5 readily resin with thealkydresinsolution. sprayed: The rind ng i9, i rntlie er vn ste must beIt is a particuiar'obiectof this invention to Carefully carried Out ii 1provide a wrinkle coating composition having a e? Vinyl 1 l 9?.12 m-3%vinyl resin-contained thereinand-which results mi i 9f til? 35 Q391395151371 a rahiexfilmion lea-king thereof; ntim nt av #9 1 21 earieu ni v L Qbiectiofithivsi inv m suitable in this respect, s noe'theST! provide a v nyl resin haste whicnmay tensed s in, the production ofa wrinkle coating cgrn go terlously e e the W Simon 5;: Thegrmclmgoperatron of th vinyl resin with It is another object ofjthisinvention to proh, alkyd resin m a i i 9n 5111175310113 vide awrinkl'e'coating comrositign m a 'in l apparatus known tothe art such-as pebblemills, resin contained therein and'whi'ch produceea @54 mi ls, vQ1?1:91:with, i eba fi v rfilm of'fin'e uniform texture. ll used it may b g tqif F fi i of Sgt is yet another object of this invention to 510 thepresent-invention. provide a pigmented wrinkle coating composilt'shouldalso be noted the polyvinyl resin thereirrand when ground into the pasteform functions as an which t 11 1 h ggfie d g'tg; b k inenttpiginentntherein and the necessity tor'utimg tsmpqmmres r Ii ZiI-Ignthgusual pigmentation by means of talc,

It S 11 an ther Object of thisinventionto asbestine;; etc. issubstantially eliminated. Whenthe final composition is sprayed to form afilm the inert polyvinyl resin upon subsequent baking of the film ismelted by th heat and becomes an integral part of the film, thusmodifying the characteristics of the alkyd resin and producing a finewrinkle pattern of hard, scratch proof structure.

The texture of the resultant film is dependent to a degree upon theratio of the amount of polyvinyl resin used to the amount of alkydresin. This ratio calculated on a weight basis of the solid content ofthe two resins may vary between 1:1 and 1:10, although a content ofpolyvinyl to alkyd of about 1:5 is preferred. If an excessive amount ofvinyl resin is used th texture of the resulting film becomes almostmicroscopic and the film itself presents a dull appearance.

In the accompanying drawing a flow sheet is presented which illustratesthe various steps of the preferred methods of the process for making thecoating composition of my invention.

The following examples taken in connection with the accompanying flowsheet may be considered as exemplary of the compositions and methodsparticularly employed in connection with the present invention.

Example I A brown pigmented vinyl-alkyd resin wrinkling coating wasprepared as follows:

(a) A cooked oil extended modified alkyd resin was first preparedcontaining parts by weight as follows:

This resin is dissolved in a thinner such as xylol to form alkyd resinsolution-1. This solution contains approximately 60% resin and 40% xylolby weight.

(b) A vinyl paste was then prepared by grinding together the followingparts by weight:

Vinyl paste-1:

Commercial polyvinyl chloride resin (1 to 30 microns in diameter) Alkydresin solution-1 8 Total 12 The abov paste is stable and may be storedfor a time before using.

(c) A paste for the pigmentation of the wrinkling composition to beproduced was then prepared by mixing in parts by weight the following:"

Brown paste-1:

Burnt umber 5.0 Titanium oxide 2.5 Calcium carbonate (Multifex) 3.5

Dicalcium silicate Alkyd resin solution-1 Dicalcium aluminate]I Ceme 2664Q Total 43 (d) A brown pigmented vinyl-alkyd resin Wrinkle compositionwas then formed by mixing while agitating the following in parts byweight:

Brown paste-1 Alkyd resin solution-1 123 Vinyl paste-1 54 Cobaltnaphthenate 6% 3 Butanol 15 Toluol 75 Total 360 The weight ratio ofvinyl resin to alkyd resin in the above mix is 1 7.25.

The wrinkle composition so formed when sprayed on a metal panel andbaked for 30 minutes at 300 F. yielded a uniform fine wrinkle pattern.

It should be noted that the use of polyvinyl chloride in the aboveformulation results in a material reduction in baking time over thatnormally required, that is, 45 minutes at 300 F. as contrasted to 30minutes at 300 F. in the present instance.

Non-volatiles 49-51% Solventcoal tar and petroleum solvents. ViscosityU--W Acid 12-18 Weight, per gallon 7- 7 lbs.

(1)) A vinyl paste was then prepared by grinding polyvinyl chloride as afine white powder into the solution of (a) above, in parts by weight asfollows:

Vinyl paste-2:

Alkyd resin solution2 8 Polyvinyl chloride powder} 4 1-30 micronsdiameter Total 12 Blue paste-1:

Magnesium silicate 4 Cobalt blue 4 Alkyd resin solution2 8 High fiashnaphtha 2 Total 18 The blue pigmented vinyl-alkyd resin wrinklecomposition was then achieved by mixing while agitating, in parts byweight:

The above composition when baked and sprayed on a metal panel gave afine wrinkle texture.

The ratio of vinyl resin to alkyd resin by weight in the abovecomposition is 1:6.

mangoes? Example III Another .blue pigmented vinyl-alkyd resin.wrinkling composition was prepared as follows: (a) Vinyl paste-3:

Parts Vinyl chloride, 95%. 4 Vinyl acetate, 5% m Alkyd resin solution-28 Total 1 2 Blue pastes-1 90 Vinyl paste3 60 Cobalt naphthenate 6% 3Alkyd resinsolution-Z 160 Toluol. 57

Total 370- The ratio, of. yinylresin to. alkyd resin by weight inrthe.above composition is a 1 6.. l

The wrinkle composition sprayed well and when :baked produced ahardscratch-proof film in minutes at 3.00F. Tnis'film, as in each oftheother :examplesgivemwas Iron-thermoplastic.

I have thus described severalspecific examples for the production of.awrinklingresin composition utilizing a vinyl resin paste.

Itwill be. apparent to those skilled in the :art

at myinvention isnot limited to the specific colored wrinkle finishes asset forth herein, but that substantially any color of wrinkle finishmaybe produced by .my'novel process.

It will also be understood by thoseskilled inthe art that othermodifications of. my invention may be accomplished by proper selection.of' polyvinyl resins havingcertain properties, particularly the finelyground ieatureof the resin-,- which-permits complete and uniformdispersion throughout the vinyl paste.

It will further be understood that while there have beendescribed-herein certain specific embodiments of my invention, it is notintended thereby to have it the specific details given, in'view of thefact that this inventionis susceptible to various=modificationsandchanges which come within the spirit of. the invention and the scope of.the appended claims.

lclaim:

1.. A wrinkling finish composition comprising a finely divided vinylresin selected from the group consisting of polyvinyl chloride and vinylchloride-vinyl acetate copolymers, a wrinkling alkyd resin obtained bycooking together, by weight, about 12.28% glycerineabout 1919395,phthalic. anhydride, about 1.15% maleic anhydride, about 16.94% linseedoil acids.. about 23.12% rosin and about 26.58% tung oil, andsolvent,the weight ratio of the selected vinyl resin to the wrinkling alkydresin being from 1:1 to 1 10.

2. A wrinkling finish composition comprising finely divided polyvinylchloride resin, a wrinkling alkyd resin obtained by cooking together, by

may also be. added to the.

limited to Dr circumscribed by 23.12% resin and about pigment, finelyweight, about 12.28% phtlialic anhydride, about 1.15% maleicanhydrideabout 16.94% linseed-oil acids, about 23.12% rosin and about26.58% weight ratio. of polyvinyl chloride resin to wrinklingalkyd'resinbeing from 1:1 to 1:10;

'3; A wrinkling finish composition comprising a finely divided resinouscopolymer of vinyl .chloride. and vinyl. acetate, a'wrinkling alkydresin obtained by'cooking. together, by weight, about 12.28% 'glycerine,about 19.93% phthali'c anhydride, about 1.15% maleic anhydride, about:16.94% linseed oil acids, about 23.12% resin and about 26158% tung oil,and solvent, the weight ratioofthe resinous copolymer to the wrinklingalkyd resin being from 1:1 to 1*. 10;

4. A wrinkling finish composition comprising pigment, a finely dividedvinyl resin-selected from the-group consisting of polyvinyl chloride andcopolymers of vinyl chloride and vinyl acetate, a wrinklingalkyd resinobtained!- by cooking t0- gether, by'weight, about 12.28% glycerine,about 9.93% phtha-lic anhyd-ride, about 1.15% maleic anhydride, about16.94%

26.58% tung oil, and solvent, the Weight ratio of the selected vinylresin to'the wrinkling alkyd resin being from l'zl'to 1:10.

5. A wrinkling finish com-position comprising divided polyvinylchloride, aresin obtained by cooking together, by weight, about 1'2;28%glycerine, about 19.93% phthalic anhydride, about 1.15% maleicanhydride, about 16.94% linseed oil acids, about 23.12% rosin and about26.58% tung oil, a metal drier, and solvent, the weight ratio ofpolyvinyl chloride resin to wrinkling alkyd resinbeing about 27.25.

6. A wrinkling finish composition comprising pigment, finely dividedpolyvinyl chloride resin, a wrinkling alkyd resin obtained by cookingtogether, by'weigh-t, about 12.28% glycerine, about 19.93% 'phthalicanhyd'ride, about 1.15% maleicanhydride, about 16.94% linseed oil acids,about 23.12% rosin and about 26.58% tung oil, a metal drier,and-solvent, the-weight ratio of polyvinyl chloride to the wrinklingalkyd resin being about 1:6.

"7. A wrinkling finish composition comprising pigment, a finely dividedresinous copolymerof vinyl chloride and vinyl acetate; .9, wrinklingalkyd resin obtained by cooking together, by weight, about 12.28%glycerine, about 19.93% phthalic anhydride, about 1.15% maleicanhydride', about 1.694% linseed oil acids, about 23 2% rosin and about26.58% tung oil, a metal drier,- and' solvent, the weigh-t ratioof theresin-- ous copolymer to the wrinkling alkyd resin being about 1:62

8'; The method of making composition which comprises the step ofdispersing a finely divided vinyl resinselected from thegroupconsisting-of polyvinyl chloride and resinous copolymers of vinylchloride and vinyl acetate ina-soliition-of awrinkling alkyd resin, saidalkyd being obtained by cooking together, by weight, about' 1'2.28%'glycerine, about 19.93% ph-th'alicanhydride, about 1.15% maleicanhydride, about 16:94:90 linseed oil acids, about 23.12% rosin andabout 26.53% tong oil, the weight ratio of the selected vinyl resin tothe wrinkling alkyl resin being from 1:1 to 1: 0.

9. The method of making a wrinkling finish composition which comprisesthe step of dispersing finely divided polyvinyl chloride resin in awrinkling alkyd awrinkling finish lycerine, about 19.93%-

tung oil, and solvent, the

linseed oil acids, about solution of a wrinkling alkyd resin, said alkydbeing obtained by cooking together, by weight, about 12.28% glycerine,about 19.93% phthalic anhydride, about 1.15% maleic anhydride, about16.94% linseed oil acids, about 23.12% rosin and about 26.58% tung oil,the weight ratio 'of the' polyvinyl chloride resin to the wrinklingalkyd resin being from 1:1 to 1:10.

0. The method of making a wrinkling finish composition which comprisesthe step of disparsing a finely divided resinous copolymer of vinylchloride and vinyl acetate in a solution of a wrinkling alkyd resin,said alkyd being obtained by cooking together, by weight, about 12.28%glycerine, about 19.93% phthalic anhydride, about 1. 5% maleicanhydride, about 16.94% linseed oil acids, about 23.12% rosin and about26.58% tung oil, the weight ratio of the resinous copolymer to thewrinkling alkyd resin being from 1:1 to 1:10.

11. The method of making a wrinkling finish composition which comprisesforming a paste of pigment, a, finely divided vinyl resin selected fromthe group consisting of polyvinyl chloride and resinous copolymers orvinyl chloride and vinyl acetate, a wrinkling alkyd resin obtained bycooking together, by weight, about 12.28% glycerine, about 19.93%phthalic anhydride, about 1.15% maleic anhydride, about 16.94% linseedoil acids, about 23.12% rosin and about 26.58% tung oil, and solvent, inwhich paste the weight ratio of th selected vinyl resin to th wrinklingalkyd resin is from 1:1 to 1:10, and thinning the paste with sufiicientsolvent to obtain a sprayable composition.

12. The method of making a wrinkling finish composition which comprisesforming a paste of pigment, a finely divided polyvinyl chloride resin, awrinkling alkyd resin obtained by cooking together, by weight, about 12.8% glycerine,

about 19.93% phthalic anhydride, about .15% maleic anhydride, about16.94% linseed oil acids, about 23.12% rosin and about 26.58% tung oil,and solvent, in which paste the weight ratio of the vinyl resin to thewrinkling alkyd resin is from 1:1 to 1:10, and thinning the paste withsufficient solvent to obtain a sprayable composition.

13. The method of making a wrinkling finish composition which comprisesforming a paste of pigment, a finely divided resinous copolymer of vinylchloride and vinyl acetate, a wrinkling alkyd resin obtained by cookingtogether, by weight, about 12.28% glycerine, about 19.93% phthalicanhydride, about 1.15%'maleic anhydride, about 16.94% 23.12% rosin andabout 26.58% tung oil, and solvent, in which paste the weight ratio ofthe vinyl resin to the wrinkling alkyd resin is from 1:1 to 1:10, andthinning the paste with suiiflcient solvent to obtain a sprayablecomposition.

14. The method of making a wrinkling finish composition which comprisesthe steps of dispersing a finely divided vinyl resin selected from thegroup consisting of polyvinyl chloride and resinous copolymers of vinylchloride and vinyl acetate in a solution of a wrinkling alkyd resin,said alkyd being obtained by cooking together, by weight, about 12.28%glycerine, about 19.93% phthalic anhydride, about 1.15% maleicanhylinseed oil acids, about dride, about 16.94% linseed oil acids,about 23.12% rosin and about 26.58% tung oil, toobtain a paste, andmixing said paste with a paste,

comprising pigment, filler, and the wrinkling alkyd resin and withsufficient solvent to produce a sprayable composition, the Weightratioof the vinyl resin to the wrinkling alkyd resin in said compositionbeing from 1 1 to 1 10.

15. The method of producing a wrinkle finish coating which comprisesspraying a dispersion of pigment and a finely divided vinyl resinselected from the group consisting of polyvinyl chloride and resinouscopolymers of vinyl chloride and vinyl acetate in a solution of awrinkling alkyd resin, said alkyd being obtained by cooking together, byweight, about 12.28% glycerine, about 19.93% phthalic anhydride, about1.15% maleic anhydride, about 16.94% linseed oil acids, about 23.12%rosin and about 26.58%,

tung oil, onto a base to form a film thereon, and baking said film, theweight ratio of the selected vinyl resin to wrinkling alkyd resin in thedispersion being from 1:1 to 1:10.

16. The method according to claim 15 in which the film is baked forapproximately 30 minutes at about 300 F.

17. The method of producing a wrinkle finish coating which comprisesspraying a dispersion of pigmentand a finely divided polyvinyl chlorideresin in a solution of a wrinkling alkyd resin, said alkyd beingobtained by cooking together, by weight, about 12.28% glycerine, about19.93%. phthalic anhydride, about 1.15% maleic anhydride, about 16.94%linseed oil acids, about 23.12% rosin and about 26.58% tung oil, onto abase to form a film thereon, and baking said film, the weight ratio ofthe vinyl resin to wrinkling alkyd resin in the dispersion being from1:1 to 1:10.

13. The method of producing a wrinkle finish coating which comprisesspraying a dispersion of pigment and a finely divided resinous copolymerof vinyl chloride and vinyl acetate in a solution of a wrinkling alkydresin, said alkyd being obtained by cooking together, by weight, about12.28% glycerine, about 19.93% phthalic anhydride, about 1.15% maleicanhydride, about 16.94% linseed oil acids, about 23.12% rosin and about26.58% tung oil, onto a base to form a film thereon, and baking saidfilm, the weight ratio of the vinyl resin to wrinkling alkyd resin inthe dispersion being from 1:1 to 1:10.

WILLIAM A. WALDIE.

References Cited in the file of this patent UNITED STATES PATENTS OTHERREFERENCES I Gardner, Physical and Chem. Examinations of Paints,varnishes, Lacquers and Colors, 9th ed., May 1939, page 562, Instituteof Paint and Var! nish Research, Washington, D. C. V

1. A WRINKLING FINISH COMPOSITION COMPRISING A FINELY DIVIDED RESINSELECTED FROM THE GROUP CONSISTING OF POLYVINYL CHLORIDE AND VINYLCHLORIDE-VINYL ACETATE COPOLYMERS, A WRINKLING ALKYD RESIN OBTAINED BYCOOKING TOGETHER, BY WEIGHT, ABOUT 12.28% GYLCERINE, ABOUT 19.93%PHTHALIC ANHYDRIDE, ABOUT 1.15% MALEIC ANHYDRRIDE, ABOUT 16.94% LINSEEDOIL ACIDS, ABOUT 23.12% ROSIN AND ABOUT 26.58% TUNG OIL, AND SOLVENT,THE WEIGHT RATIO OF THE SELECTED VINYL RESIN TO THE WRINKLING ALKYDRESIN BEING FROM 1:1 TO 1:10.